PREPARATION  OF 


ORTHO  AND  PARA  CHLORTOLUENE 
PHEN  LY  ACETALDEHYDE 
DIPHENYL 

BY 


JESSE  RAY  JOHNS 


THESIS 

FOR  THE 

DEGREE  OF  BACHELOR  OF  SCIENCE 

IN 

CHEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 
UNIVERSITY  OF  ILLINOIS 


1921 


JC;*^a»<ta-  - ^.'s»^^«;To-«b.««.  'I-^'  iTnunwiiriT  ■ ;. 

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ACKNOWLSDG-EI.IENT . 

The  author  wishes  to  express  his  thanks  and 
appreciation  to  Dr,  ROG-ER  ADAMS  thni  whose  helpful 
suggestions  and  criticisms  this  work  has  been  made  possible. 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/preparationofortOOjohn 


PS 

CONTENTS 

I Introduction, 

II  History  and  Theory, 

A,  Phenylacetaldehyde,  I 

B Ghlortoluene,  9 

C , Diphenyl  1 2 

III  Experimental, 

A,  Phenylacetaldehyde.  4 

B , Diphenyl . 1 3 

IV  Discussion, 

A,  Phenylacetaldehyde,  7 

B,  Diphenyl.  19 

C , Ohio  r t o ill  en  e . 11 

V Conclusions. 

A,  Phenylacetaldehyde,  8 

B,  Diphenyl,  20 

VI  Bibliography,  21 


INTRODUCTION 


The  work  of  the  semester  was  divided  between  three 
different  subjects.  The  first  subject  investigated  was  the 
preparation  of  phenylacetaldehyde.  This  aldehyde  has  a 
very  distinct  hyacinth  odor  and  is  used  a great  deal  as  a 
perfume.  The  ordinary  '^aethods  of  preparing  this  aldehyde 
are  very  expensive.  It  v/as  with  the  idea  of  trying  a 
comparatively  cheap  catalytic  reduction  method  that  this 
v/ork  was  attempted. 

Two  test  runs  of  aa  process  for  the  preparation  of 
ortho  and  para  chlortoluene  were  made.  The  directions  do 
not  appear  in  printed  form  but  were  furnished  by  Dr, 

Adams , 

Diphenyl  has  been  made  by  ineffective  catalytic 
methods  ever  since  it  was  discovered,  A new  catalytic 
method  has  been  described  by  Dr.  James''  that  appears  to 
be  very  effective.  This  work  on  diphenyl  has  been 
limited  to  improvements  on  the  method  described  by 
Dr.  James, 


1. 

THE  SYNTHESIS  OF  piraYLACETALNEHYDE. 

I.  THEORETICAL  DISCUSSION. 

Phenylacetaldehyde  has  a distinct  hyacinth  odor  that 
makes  it  valuable  in  perfumes.  It  appears  on  the  market 
in  a solution  of  benzylbenzoate  as  "jacinth".  This  aldehyde 
is  a syntheyic  product  and  does  not  appear  in  the  natural 
hyacinth  perfume, 

Phenylacetaldehyde  can  be  made  by  three  distinct 
methods.  First,  the  reduction  of  phenylaceticacid;  second, 
the  G-rignard  reaction;  third,  the  decomposition  of  hydroxy 


acids . 

The  classical  method  of  preparing  aldehydes  is  to 
heat  the  calcium  salt  of  the  acid  with  calcium  lorniate. 


The  acid  is  reduced  to  the  aldehyde  and  calcium  carbonate 
is  formed  according  to  the  reaction. 


This  reaction  is  not  clean  cut  and  the  yield  of  aldehydes 

of  high  molecular  weight  is  very  unsatisfactory,  So^uibb 
2 

and  Ipatief  tried  to  improve  this  reaction  by  using  the 
salts  of  different  metals  than  calcium.  Instead  of  forming 
the  salts  first  and  then  heating  them  they  passed  the 
mixture  of  acids  thru  a heated  tube  partially  filled  with 


the  metallic  carbonate  or  oxide.  They  found  that  the 


foiTTiic  acid  decomposed  at  a temperature  belov/  onat 
required  for  the  reduction  of  the  acid  so  that  their 
results  v;ere  unsatisfactory.  Later  Sabatier  and  Senders 


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2 


while  working  on  the  catalytic  preparation  of  aldehydes 

found  that  the  use  of  titanium  oxide  would  allow  the 

acid  to  be  reduced  at  a low  enough  temperature  so  that 

the  formic  acid  could  be  used.  In  a later  paper  they 

suggested  the  use  of  manganous  oxide^  as  an  imprivement 

over  the  use  of  titanium  oxide  or  any  other  metallic 

oxide  that  could  be  used.  This  oxide  was  claimed  to  reduce 

acids  of  high  molecular  weight  very  readily, 

Ph eny lac etaldehyde  can  also  be  prepared  by  means  of 

the  G-rignard  reaction.  The  benzyl  magnesium  halide  compound 

7 

can  be  treated  either  with  formic  acid  and  decomposj^ 


.fir 


vd' tL  T/-at ei  to  fcrr.  phenylac etaldehyde. 

It  0 

or  formic  ester  and  deconpose!-'  v/ith  water  to  form  the 

G 

aldehyde.  This  reaction  besides  being  expensive  gives 
very  poor  yields^ 

The  great  bulk  of  the  work  on  the  preparation  of 

phenylace  b^?,dehyde  has  been  done  on  the  preparation  and 

decomposition  of  oxy  acids  to  form  the  aldehyde, 

9 

In  1884  Glazer  while  working  with  Erlenmeyer 
distilled  a solution  of  phenyl- lactic  acid  in  potassium 
hydroxide.  An  oil  came  over  that  Bayer  identified  as 

pheny lac etaldehyde.  Very  soon  after  this  Lipp^^and 

1 1 

Hamburger  took  up  the  study  of  this  reaction  as  a 
means  of  preparing  the  aldehyde.  Phenyl- lactic  acid 
itself  was  not  used  but  its  chlor  derivative  or 


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its  hydroxy  derivative,  phenyl  glucidic  acid  was  used. 

The  starting  point  for  the  preparation  of  these  tv/o 
acids  v;as  cinnamic  acid  in  all  cases. 

Cinnamic  acid  when  treated  with  hypochlorous  acid 
unites  directly  with  it.  The  double  bond  in  the  cinnamic 
acid  becomes  saturated  to  form  a chlor  lactic  acid,  thus: 

If  the  chlor  lactic  acid  is  treated  with  a strong  alkali 

a 6) 


phenylglycidic  asid  salts  ai*e  formed. 


Ac-  c _ C OH  — ) 

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0^  * - - . 

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phenylglycidic  acid  readily  decomposes  into  carbon  dioxide 

> C:> 


V 


and  the  aldehyde,  thus:  ^ C 


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A great  deal  of  difficulty  was  encountered  by  these  men 
in  producing  hypochlorous  acid  free  from  chlorine.  The 
free  chlorine  in  the  hypochlorous  acid  used  attacked  the 
benzene  ring  and  produced  chlor  derivatives  of  the 
aldehy  de,  Bamburgerl 1 freed  his  hypochlorous  acid  by 
treating  a solution  of  sodium  hypochlorite  ¥^ith  boric 


acid,  Glazer  used  carbon  dioxide.  None  of  the 


12 


methods  produced  an  aldehyde  free  from  chlorine, 

13 

In  1910  Erdmann  patented  a process  in  which  he  claimed 
to  have  proauced  a lactone  of  propionic  acid  by  the 

14 

action  of  hypobromic  acid  an  cinnamic  acid,  Diekmann, 
however,  proved  that  the  lactone  is  nothing  other  than 
the  potassium  salt  of  phenylglycidic  acid. 


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4 

EXPERIIv^ENTAL  PART. 

1 "5 

Erdmann's  process  for  the  preparation  of  phenyl- 
glycidic  acid  was  used  as  the  representative  reaction 
for  the  preparation  of  the  oxy  acid  used  in  the 
preparation  of  phenylacetaldehyde.  50  gms.  of 
cinnamic  acid  v/as  added  to  'J>G  gms,  of  50/^  KOK  and  500 
gms.  of  water.  This  v/as  evaporated  to  160  c.c.  and 
allowed  to  cool,  100  gms,  of  50^  KOH  was  mixed  with  70 
gms.  of  ice  and  cooled.  73  gms.  of  bromine  were  nin  into 
the  cooled  gOH  solution.  After  all  the  gromine  was  aaaed 
10  gms.  of  KOH  solution  was  added  to  remove  as  much 
free  broiiiine  a,s  possible. 

The  cooled  potassium  cinnamate  solution  was  then 
mixed  with  500  gm*s , of  ice  and  the  potassium  hypobromite 
liquor  added.  After  stirring  the  mixture  well  70  gms. of 
boric  acid  was  added  to  free  the  HBrO,  The  reaction  is 
complete  in  an  hour.  At  that  time  the  mixture  was  made 
alkaline  to  precipitate  out  the  potassium  salt  of 
phenylglycidic  acid,  4o  gms,  of  the  potassium  salt  was 
formed.  On  acidifying  this  potassium  salt  and  distilling 
the  resulting  solution  13  gms.  of  phenylacetaldehyde 
was  formed.  Yield  26^, 

Most  of  the  work  of  the  semester  was  centered  on 
the  reduction  of  phenylacetic  acid  to  phenylacetaledhyde. 
Manganous  oxide  was  used  as  a catalyzer,  A furnace  of 

15 

the  type  described  by  Rogers,  Marvel,  and  Kamm  for 
the  preparation  of  amylene.  The  temperature  of  the 


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5 


reaction  carried  on  in  the  furnace  did  not  rise  above 
350  C at  any  time  so  that  careful  Insulation  was  not 
necessary. 

The  furnace  consisted  of  a three  foot  section  of 
two  inch  iron  pipe  wound  with  50  turns  of  #16  ni chrome 
wire  and  insulated  with  asbestos.  Over  the  resistence 
wire  winding  was  placed  a section  of  asbestos  steam 
pipe  covering.  The  temperature  of  the  furnace  was 
regulated  by  the  use  of  a pyrometer. 

In  all  cases  the  phenylacetic  acid  was  dissolved 
in  the  formic  acid  and  introduced  into  the  furnace 
thru  a dropping  funnel.  The  ratio  of  three  parts  of 
formic  acid  and  one  part  of  phenylacetic  acid  was 
decided  on  at*  giving  the  best  results.  The  catalyst  in 
all  cases  was  manganous  oxide.  Pieces  of  pumice  stone 
were  coated  with  wet  manganous  carbonate  and  introduced 
into  the  furnace  in  sufficient  amount  to  fill  the  pipe 
loosely.  The  furnace  temperature  was  then  raised  to  300 
and  methyl  alcohol  was  passed  in  to  form  the  oxide. 

In  no  case  was  a satisfactory  yield  of  phenyl- 
acetaldehyde  formed  by  the  use  of  this  furnace.  The 
temperature  of  300-325  C suggested  by  Sabatier  was  found 
to  be  the  only  one  that  gave  any  results  at  all. 

The  fomic  acid  used  in  these  experiments  varied  from 
50^  acid  to  90^.  The  use  of  the  50^  acid  gave  only  a 
very  high  boiling  oil  and  no  aldehyde.  The  90^  acid 
gave  n ot  more  than  a 9^0  yield  as  a maximum.  As  the 


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6 

/ 

anhydrous  formic  acid  could  not  be  obtained  at  the 
store  room  the  pure  acid  was  not  used. 

3 

Sabatier  and  Senders  also  claimed  that  this  catalytic 
reaction  is  also  very  satisfactory  for  the  preparation  of 
esters.  Using  1 mol  of  amyl  alcohol  and  2 mols  of  glacial 
acetic  acid  a 70^  yield  of  amyl  acetate  was  produced 
in  a test  run. 


^m.  -«  -K 


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7 

DISCUSSION. 

The  reaction  as  carried  on  by  the  author  v;as  not 
at  all  satisfactory  at  any  time.  The  failure  of  the 
reaction  was  not  due  to  any  known  cause.  Reactions 
with  different  purities  of  the  formic  acid  seemed  to 
indicate  that  the  amount  of  water  in  the  reaction  had 
something  to  do  with  the  yield  of  the  aldehyde  but  not 
enough  to  account  for  the  greater  part  of  the  impurities 
formed  in  the  reaction. 

The  liquid  coming  from  the  furnace  did  not  contain 
any  free  formic  acid  and  only  traces  of  phenylacetic  acid. 
The  great  bulk  of  the  acid  was  decomposed  to  form  a 
sticky  very  high  boiling  oil  of  varying  boiling  point. 

As  this  reaction  was  carried  on  in  the  original 
experiments  in  a glass  tube  and  the  formic  acid  and 
phenylacetic  acid  passed  into  the  tube  in  vapor  form 
sej^arately  the  method  might  be  differer.t  enough  to 
cause  all the  change  in  yield. 

No  means  of  carrying  the  original  experiment  out 
wa.3  available  otherwise  a comparison  of  results  would 
have  been  made. 

The  easy  preparation  of  amyl  acetate, however, 
showed  that  the  apparatus  as  set  up  might  be  a very  good 
method  of  making  esters. 


1 BTjJr  fl' V ' ' W-^  V*  #’‘*.  ' •-  « 'Vk 

L^¥^-  - ^".'^fei?,  ^^V'_,:.,  ft.  ,t^V.  ' , * -.V  '.  ■ yv.  ^ r,v3fl 

TA 


:•?  -ji  */. 

■T.'  ^ 


* ■*.' 


■V  t;* ' ,'  id  JV<i' Q* . 

, ^ -:  >;•  V,  ;•  '-.Hi^'''^^'-  .,  ■ ’:-;^i*;^S' “ , 

.■  ..  ^^r.-.'*  ■"’■  ^ V '-■:'  ■:■  J'\  ■■  . .. V'/ 

•■  ^','*c>Jl<^^i  .//'  V*lfc;V  j.:n 

■•  ' ",  , • ^ 'W'^lil’^  ■:',C'’  ■'•^' 

*0y.  ■■^ih^C.OT 

V _ ■ •'  • •;?'  '.  ^V.'  - . . 

411^  Mi  *tWAi7f4'rt;p^feLf^^ 

'■„  • : ■ -'.  ■ ■ : ■.^..v  , *^r'  • ■■  - ' 

*■’"'’  '■  . ■ /?  ’ f •/»''%.•. n‘ 't/  Ti'  r’ 

‘-  ky.tfi,  Yt>  0 i^f>%  fSivoi^i>4^pi^--  *«^S* 

f.,  ■■  -I*  -v'-' 


ift- 


. . . ' ' .a 

.4ruiw;  ^i?rvic<f'.*?}i(^ivi'«V'-lo  ' c^i^iii' 

, -V-  K ' ■’’ 


r-'-ri 


*'.'• : » ' ' ' . ^'  , '.  ■ ' .v'l  , " •?-:/■ : ' '■  ,•;,  ' ■.  *■'?'•;/; , ' ,.' ' ; zS  . - 

. ' ,^tt*  ni#'.  &,..  ■tci'i  .<fl^  t'A..* '«CM  «■£&'  1"  i!U’'«ttffe*fet»)ij^' 

' 040'-  i*f?i  > ,j*5^! 


/-I  '•  y ^ ' , ,|« ».  . rv  ' •••a  V.  '■  .a*,-  , _ J.*’ilL  ' •■ 


t flS  XS  '■  v"' 


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V V- . . 


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'■  ILI*'  ■ vl'* 


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■ ■>■ ./--.  ; 


8 


CONCLUSION 

The  results  obtained  in  the  attempted  catalytic 
method  for  the  preparation  of  phenylacetaldehyde  show 
that  the  method  used  cannot  be  made  practical  without 
some  very  great  improvements. 

The  author  believes  the  failure  of  the  reaction  was 
due  to  the  following  reasons . 

(a)  Impure  acid, 

(b)  Incorrect  preparation  of  the  catalyst. 


irtrtJfe 


'c 


V.  - , j,3 


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• _ J-*  . '?»■:''' *”'ii  '.■'"i"  u^iHia 


IF*  ^VBMHnkA  ’ JkV?iF  'mV  ...  ■'^x  a ^ - 


'•  >*s. 


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'P  ■?.»’  ■ ’©-ni^^iX  . ■■  XsiR^Wi: 

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^ ' *'  ■ I * .'  - '■  -y  '^W'jn 


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fJt 


9 

SYNTHESIS  OP  ORTHO  iUID  PARA  CHLORTOLUENE. 
THEORETICAL  DISCUSSION. 

There  are  only  two  methods  for  the  prepa.'Xtion  of 
the  chlortoluene.  Chlorine  v/ill  act  on  toluene  to  form 
ortho  and  para  chlortoluene  according  to  the  reaction 


unless  very  dilute  solutions  are  used  when  the  yield  of 


The  direct  chlorination  of  toluene  is  very  greatly 


The  separation  of  the  o and  p- chlortoluene  formed  by 
the  direct  action  of  chlorine  can  be  separated  by 
completely  sulfonating  both  chlortoluenes  and  fractionally 
crystallizing  the  sodium  or  barium  salts.  Or  by 
sulfonating  out  the  o- chlortoluene  and  separating  the 


two  by  this  method, 

A test  run  on  the  direct  chlorination  of  toluene 
was  made  in  the  following  manner; 

In  a 5 liter  flask  fitted  with  a good  reflux  condenser 
and  mechanical  stirrer  was  placed  1650  gms,  toluene  and 
18  gms.  of  powdered  iron.  Chlorine  was  passed  into  the 
toluene  until  the  specific  grayity  reached  1,o6,  The 
time  of  chlorination  was  about  8 hours.  After  chlorination 
the  liquid  was  fractionated  direct.  The  part  coming  over 


1 f\ 

The  diazo  reaction  is  also  used'  but  the  yield  is  poor 


accelerated  by  the  use  of  iron  or  other  metals 


19 


4 • 

. vV  ■■ 


> r 


H'  . 


'“t  • ■ 


);:;x 'X/.. 


’ .'  «-1 


1 frO 


•^(Y.  f.yj  71 -: 


- 'W  ■ . 

- ■,  :• 

. • ' ’I  ■ r •*»'' 

. •lOM/.rvrJ-  it/Xl'-  •T'iJ  • Vt 

" V.  ;,t  ?■' 


‘ '.  ' i ' 


r .,---  ? f . ' V , 


/ < 


IJ. 


•'•'■■’v,»j  V- 

'»  4«r  -.•  4 ‘• 

»'  ••  V ' ••  . ' ■ • 

'■  .'  ,;,r/^r' 

■ ■'  ' ' • ' ■ ' ■'  ■ '/') '. 

* ’ .'  Anto|f»wVf>Xy-  --V  „ ; 

,.  ,.  ■ f* 


'ill  ’ V • •■>,„^l;,t  » .j 


' -■.)  -t 


C *’i'J  T'^'-ts^AV 

<«■■'  , ■ ' ••5  .<, 


r.. '.'  . : ■ ;r 


-.o-'  s'.')t>'c;.A"^«4kd 

.'♦•’•rfsi  i. 


- J w ■ * •*  • 


-•'i/f.'  V 'i:  s,'  - .••aoU’  f'':  t' "./ vXk.a-^ 


‘ci  I . *.  iT...'n’  ■',  n,  , ; r ■■ «., 


i. 


•:iai‘:,\  . v":V*j'iiW'-n'.  .'da  J ;*  nJ*-  . / 


" a 


. ix:>Y  \rjS 

j,  ’ i . . . , • ' » «’i 


« t 


»-  ■ ■» . 


. t 

/ . 


i ■■  ■ '."  ;'i  '.'''y.  i,.f<'r' ■- 

'■y*'  -I  -.  ►.  f'  . 43  - 


i ■ 


lu>  fo.y  . 

*’  . ' . f - -I'u ' 


• * '•'  ''-i.i'toS:'  . iivrS: ' . '%' 


Y'f.i 


' y 

■>  J'  u . ,'  V #i(-  ; 


• ' ' " '1::  V i.' ill' io  r ,V»  ■ n 


H i*- 


11  «.r  . ; i,. 


' '.cX  ■/'  ■-t'XXiP  :’  ''-b- 


^ V < ,t 


10 

below  was  considered  unchlorinated  toluene  and  amounted  to 
300  c,c.  The  fraction  coming  over  between  150-  160  C was 
a mixture  of  the  monochlortoluenes , This  fraction  had  a 
volume  of  1600  c.c.  The  fraction  above  160  consisted  of 
dichiortoluene  and  had  a volueme  of  125  c.c. 

The  monochlor  fraction  was  then  treated  with  an 
equal  weight  of  concentrated  sulf'.ric  acid, After  stirring 
the  sulfuric  acid  mixture  for  8 hours  on  a water  bath  the 
sulfuric  acid  layer  was  drawn  off  and  an  eo_uai  weight  of  fre 
fresh  acid  was  added. This  process  was  repeated  three  times. 

The  sulfuric  acid  now  contains  all  the  ortho  chlortoluene. 

The  unsulfonated  layer  was  washed  with  dilute  sodium  carbonate 
and  then  with  fresh  vtrater  and  distilled.  The  fraction 
boiling  at158-6o  was  p-chlortoluene.  The  yield  v/as  56o 
gms . 

The  sulfuric  acid  layer  was  diluted  with  an  equal 
volume  of  water  and  heated.  At  200  the  mixture  Vfas  rapidly 
steam  distilled.  The  sulfonic  acid  became  decomposed  and 
the  ortho  chlortoluene  regenerated,  544  gms,  of  o-chlor- 
toluene  were  produced. 


It 


CONCLUSION. 

The  results  were  quite  comparable  with  those 
given  by  the  authors  (Clarke  and  Ogden),  The 
percent  of  o-chlortoluene  recovered  was  less  than 
that  given  by  them  but  this  was  due  probably  due  to 
a slov/er  saponofication  of  the  sulfonated  mixture 
and  therefore  a greater  percent  of  decomposition 
of  the  o-chlortoluene. 


V;'' 

'ilfcrri  ~"'t"f 


* ’''^v;.i:iv  . .., 


'.  ’ . ' '<s  t h 
-.c  /tip; 


-.-. . if 


■ > 


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i '•  * ■*':  ^ . I i .V  P'  ■ 1^  ‘ i 


f 


t; 


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in^ 


t . 


Lit 


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.1  ■*  ^ ■•  * ‘ ■ 

, jy"  'W,  .* 

*■-  - 


4i 

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':'■:  ;’':.4-,i^  ^ -iRr*-  ;''  C\ 


^ V - ..  , -4,  .;,:iv4,#^- 


r*^-aw=— jtsrse^  / ■> 


12 


PREPARATION  OF  DIPHENYL 
THEORETICAL  DISCUSSION. 

Diphenyl  is  made  commercially  by  passing  benzene 

vapors  thru  a red  hot  iron  tube.  This  is  the  method  used 

by  Bertholet^  original  decomposition 

3 

products  of  benzene.  Before  this  time,  however  Fittig 

prepared  diphenyl  by  treating  brombenzene  with  metallic 

5 

sodium.  Grant  and  James  found  that  by  passing  the  vapors 
of  benzene  over  a heated  ni chrome  wire  better  results 
could  be  obtained  than  by  Bertholet's  method  or  by  Fittig' 
method.  These  three  methods  are  the  only  ones  that  are 
of  any  practical  importance  at  all. 

The  catalytic  preparation  of  diphenyl  is  Just  a 
simple  splitting  out  of  hydrogen  between  two  benzenes 


is  too  expensive  in  comparison  to  the  cheaper  catylitic 
methods,  Lilce  all  the  other  methods  of  preparation  of 

diphenyl  considerable  amounts  of  high  boiling  products 

3 

are  formed  and  therefore  the  product  formed  is  no  purer 
than  that  formed  by  any  other  method. 


n im  i ■■  ■ ifTT^ 


13 


EKPERIICTTAL  PART. 

5 

The  apparatus  described  by  Grant  and  Janies  was 
first  used.  It  consisted  of  a loop  of  resistence  wire  so 
supported  in  a refluxing  apparatus  that  the  v;ire  could 
be  heated  with  an  electric  current.  Fig.  1 v;ill  better 
illustrate  this.  As  the  ni chrome  wire  described  by  Grant 
and  James  was  not  available  number  18  B&S  gague  wire  was 
used  instead.  With  a current  sufficient  to  bum  out  ten 
ampere  fuses  no  reaction  took  place  after  refluxing  the 
benzene  one  hour.  The  wire  was  not  heated  above  a dull  red 
heat,  A small  quantity  of  free  carbon  was  deposited  on  the 
wire.  Both  alternating  and  direct  currents  gave  negative 
results . 

A section  of  number  28  v^ire  was  v^ound  in  a three 
millimeter  sporal  and  heated  electrically  as  before,  Yfnen 
the  wire  v;as  heated  to  bright  redness  witha  110  volt 
direct  current  a reaction  occurred.  This  was  shovn  by  the 
elimination  of  a white  smoke  from  the  top  of  the  condenser 
and  the  condensation  of  drops  of  a brown  liquid  on  the  sides 
of  the  flask.  After  three  hours  the  excess  benzene  was 
distilled  away  and  46  grams  of  a tarry  residue  remained. 

On  fractionation  this  tar  gave  12  grams  of  a solid 
boiling  at  24C-250  , This  solid  was  diphenyl. 


I 


' *T 

Tf'  r-^- 

-.  ■ ^ ,'T  rr  * '-n  % 'It' 

K.  • *A».  V*-o 

a.  .V 

Xff>r.  "c  itii'-XC 

V'i 

*K^rf l: L. !:ijo  'lArijr),-'- 

ojTX 

i..-:  !.i'  " '. 

. ’it* 

i.^  '■  ' = > J . 

ic.  .Ajo  ,4 1 

. ‘ . f,.:  o!.,';  i'l 

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- .A'T  *•  ■ '■■  ♦ 

It /•;.■.  ‘ff.^:..' . rXi-'i  /*  . 

1 • '!ii 

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....  i . ./D-l'^l/COO  T'  ij.  „ t.'X  c'.'IO’  Ui  y oLvf'Xi.i; 

V, 

o'o  />'  ■;  :i  :or.j  .'■:  ‘In  i'.»  ic - jr2y»i£« 

■'-Lr  xmrxf  ; ■/(>•:  > '.  o unlJ.'in- ' ■^xo;.'  » a.'' 

i ’ ! .' j o ‘ j I *■  'j' 'X'*; •-  . . , - . .*  « \j j v*.>  0 


. ->j  /.'•  -( 


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- i!  c 


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jl;  - 


r.,-r-Tiyi  pniitj 


14 


The  results  of  four  runs  are  tabulated  below. 


l(7t , tar 

Wt,  diphenyl. 

foyleld. 

48 

12 

25 

51 

15 

29 

50 

14 

28 

55 

17 

31 

Sixty  cycle  alt 

emating  currents  gave 

practically 

results , 

\7t , tar 

Wt,  diphenyl 

^yield 

45 

10 

22,5 

42 

9 

21,4 

47 

10 

21,3 

44 

1 1 

25. 

In  all  probability  the  differences  in  the  percentage  of 
diphenyl  formed  was  due  to  differences  in  temperature  of 
the  wire  and  not  to  any  differences  in  electrical  effects 
of  direct  and  alternating  currents. 

After  the  benzene  vapors  passed  over  the  heated 
ni chrome  wire  they  were  so  hot  that  they  decomposed  the 
cork  in  the  neck  of  the  flask.  The  condensed  benzene  and 
diphenyl  rtinning  down  over  the  sides  of  the  hot  flask 
also  caused  considerable  trouble  by  cracking  the  glass. 

It  was  also  apparent  after  the  preliminary  runs  that  the 
diphenyl  percentage  in  tar  was  too  low  for  the  amounts  of 
tar  produced.  The  apparatus  in  Fig, 2 was  devised  to 
improve  some  of  these  difficulties. 

The  hot  wire  was  suspended  in  a tube  free  from 
the  flask  and  so  arranged  so  that  the  condensed  benzene 


.r 


'OftUwO  V.  Jv.q/.*'.  '.':r 


•> 

hu  X : 


? 


♦ < ,{‘;'ortg  t-tr.  ■?rii’x  'io  ' . r' 

. iX  ,siW  .u 


> 


Tf 


v--;^ 


c:2 


. iv 


i ; 


. w'  i- 


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, / 

Misjro'iir  U 01!^  lu  r.l 

":•  i.>  o-  eni;.  .;o.  'toX  Xvr.r;frio 

1 -r.,;  Jcn'^iJia  --flvr  • 

n OK  ; "orX'  c-'t OijX'L 

* ■>: '-i . . I ‘j.  '»:<.(■  \:-  i, 

'h'.  i..^,  ■jftJ’  *‘;'r  yo  rirroj,  '^"X'-- 

viT  jvri:o';J‘  a'i.?»r;T>o  /4-/ ■■i.iuji.-o  caSu 

M.J  J. .,  j "I-IJ.-  li  .:.,f  orJ-  on.  .3.  ;5;;>y  \ri 

•7 

'Mr-ji./,  ,,v/  '•,•('■.  v‘cx  fU’X  -1. '•■  ni  Xyni'’if^ 

•.  I 

cy  : r.  - xv^i'-o  xil  e:jrtT  . 5(5)ojxbo*-X(7 

. ■'  Mht.'r’J’  'Io  onTO!3  '>vo*?Lq 


•.  -'X.'-3W  ’. 

nas’'  ■ 

■ 1 Ov- ,■;]•/ J 

-f'OO  '' 

‘I  j-o 

.'  X»j;w 

'.  <•/  'Hi.  i. 

il'X  T' 

v\,r 

-.  ( ' 


: '..n;  ^‘:s.-:r  Jf-d 

. C)c>  vi>  f'j  c a ^ ^ ,y  ..’'T  (Vl  iif‘'J.-  '<0'i ' ; ‘ 


15 


returns  to  the  flask  thru  a separate  tube.  The  wire  v/as 
suspended  as  far  from  the  cork  as  possible  to  eliminate 
the  decomposition  of  the  cork  as  much  as  possible.  The 
connection  between  the  flask  for  refluxing  the  benzene  and 
the  tube  containing  the  hot  wire  served  also  as  a 
fractionating  column  to  keep  as  much  of  the  diphenyl 
already  formed  from  again  coming  in  contact  with  the 
catalyzer.  Trial  runs  showed  that  this  apparatus  was 
a great  improvement  over  the  first  apparatus, 

Wt.  t ar  Wt,  diphenyl  ^yield 

48  25  52 

55  51  56 

The  disintegration  of  the  cork  was  not  prevented, however, 
and  the  tar  from  the  cork  proved  very  objectionable.  The 
diphenyl  fractionated  from  this  tar  kept  the  odor  of  the 
burned  cork  even  after  a second  fractionation  and 
crystallization  from  alcohol, 

G-reat  difficulty  was  experienced  with  the  resistence 
wire  used.  It  was  necessary  to  heat  the  wire  almost  to 
its  melting  point  to  cause  the  condensation  of  the  benzene 
At  this  temperature  a great  deal  of  sagging  takes  place 
and  there  is  much  magnetic  attraction  betvmen  the  sides 
of  the  loop  so  that  the  wires  are  drawn  together  and  short 
circuting  takes  place.  When  the  hot  wire  is  cooled  below 
the  temperature  of  condensation  of  benzene  excessive 
carbonization  of  the  wire  takes  place.  This  phenomenon 


* I ^7.  • 


:-  .. , aJi,.r;i6K>{tietfi^ 


K 


I'  ■• 


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pen  u r..I  /:v 

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occurs  if  the  hot  wire  comes  in  contact  with  a cold 
support  or  the  outside  of  the  tube.  The  wire  tends  to  be 
covered  with  soot  at  the  cooled  portion  and  tends  to 
spread  over  the  wire.  It  is  therefore  impossible  to 
support  the  heated  loop  at  its  mid  portions  to  keep  the 
loop  compact . 

To  overcome  the  difficulty  given  by  the  cork  and  to 
add  a larger  fractionating  column  to  the  apparatus  to 
keep  the  diphenyl  down  the  apparatus  in  Fig.  5 was 
devised.  The  entire  apparatus  was  made  of  pyrex  glass 
by  Dr.  Anders. 

In  experimenting  with  this  apparatus  large  amounts 
of  of  diphenyl  were  not  desired.  The  lengths  of  the  runs 

were  cut  to  about  two  hours . 

There  are  definite  limits  of  temperature  for  the 
best  preparation  of  diphenyl.  At  apxjroximate  cherry  redness 
the  Wire  is  quite  rapidly  coated  with  carbon  and  ceases  to 
be  active  as  a catalyzer.  If  the  temperature  is  raised 
carbon  does  not  co3.lect  on  the  wire  and  there  is  a slight 
smoke  given  off  thru  the  condenser.  At  still  higher 
temperatures  much  smoke  is  formed  ana  the  wire  is 
rapidly  decomposed.  The  data  below  shows  the  effects 
of  different  temperatures.  (At  the  lowest  temperature) 

Benzene  used  &ms . tar  Gms. diphenyl  ^'^penzeSe  . 

56  16  11.5  72.5  28.6 


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17 


At  decomposition  temperaU..-e  of  v/ire. 

Benzene  used.  Ut.tar  Wt.  diphenyl,  ^diphenyl  jJdiphenyl 

DSnZt  Gli0 

65  13  7 54  11 

This  data  shows  quite  conclusively  that  the  best 
temperature  for  the  reaction  is  the  lowest  possible 
temperature  to  carry  on  the  reaction  or  sliglitly  above 
that  necessary  to  keep  the  wire  free  from  carbon.  At  this 
temperature  practically  no  smoke  is  formed  and  the  solids 
are  quite  free  from  large  amounts  of  free  carbon. 

Even  at  the  best  temperature  for  the  reaction  the 
wire  becomes  coated  v;ith  a black  shell  that  resembles 
oxide  and  Is  probably  a carbide  of  nickel.  This  coating 
does  not  seem  to  interfere  in  any  way  with  the  speed  of 

the  reastion. 

It  was  found  that  the  rate  of  formation  of 
diphenyl  varied  directly  as  the  lengtl  of  the  wire.  A 
foot  section  of  ni chrome  wire  vfill  produce  about  15 
grams  of  diphenyl  per  hour  while  a 4 foot  section  will 
produce  about  50  grams  per  hour.  As  the  surface  of  the 
Wire  varies  directly  as  the  length  the  yield  must 
be  dependent  on  the  area  of  the  wire  exposed. 

using  the  best  conditions  found  up  to  this  time 
a series  of  three  runs  were  made  to  determine  the  best 
possible  yield  of  diphenyl  from  the  amount  of  benzene 

used  in  the  reaction. 


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18 


Wt,  benzene 

tarCnot  diphenyl)  Wt. 

diphenyl . 

^diphenyl 

solids 

56 

6 

16 

72.5 

40 

1 1 

42 

81 

40 

2 

Wt.  diphenyl  on 
benzene  used, 
28,6 

30 

50 

12 

85 

Glilor  "benzene  was  used  in  one  run  in  place  of  ben^  n , 
the  resultins  product  was  not  ohlordiphenyl  but  HCl  split 
off  and  diphenyl  was  formed.  Toluene  in  the  same  apparatus 
decomposed  with  the  elimination  of  large  amounts  of  soot 


that  quickly  clogsed  the  apparatus. 

Nickel  wire  was  used  in  a fev;  of  the  runs  hut  it 
so  soft  When  heated  that  it  caused  a great  deal  of  trouble. 
The  results,  however  approximated  those  with  niohrome  wire. 
Tungsten  wire  was  used  in  one  run  but  the  wire  became  so 
completely  carbonized  in  a few  minutes  that  it  ceased  to 
have  sufficient  reslstence  so  that  it  coula  be  heated  to 
the  proper  temperature. 


V. 


19 


DISCUSSION, 

The  foregoing  experiments  proved  quite  conclusively 
that  the  method  for  the  preparation  of  diphenyl  studied 
equals  and  probably  surpasses  any  method  in  common  use 
for  the  preparation  of  diphenyl,  A study  of  the  data 
shows  that  there  is  a very  great  loss  of  benzene  in  the 
reaction.  There  is  no  smell  of  benzene  in  the  gases  given 
off  thru  the  condenser  so  the  benzene  must  be  decomposed 
and  given  off  as  some  decomposition  products  of  benzene. 

No  attempt  was  made  to  analyze  the  gas  and  determine 
what  the  decomposition  products  v;ere.  If  some  other 
catalyze^  can  be  found  that  will  work  at  a lower  temperature 
the  reaction  can  be  much  improved  for  in  all  probability 
at  a lower  trmperature  much  less  benzene  v/ill  be  lost 
by  decomposition. 

This  reaction  can  be  improved  still  further  by 
cut  ting  the  time  of  contact  of  catalyzer  and  benzene 
as  short  as  possible.  This  can  be  done  by  passing  the 
vapors  of  benzene  over  the  heated  wire  perpendicular 
t o the  wire  and  not  along  the  wire  as  was  done  in 
most  of  the  experiments  tried.  The  diphenyl  will 
be  given  less  time  to  condense  with  itself  and  produce 
the  undesirable  higher  boiling  fraction  of  the  tar. 


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20 


CONCLUSION. 

nth  the  apparatus  used  and  a nickel  Vvire  as  the 
catalizer  the  yield  is  approximately  at  a maximum. 

The  60/^  loss  of  benzene  in  the  reaction  cannot  be 
avoided  unless  soiAe  new  catalizer  is  used  that  will 
cause  the  reaction  to  teke  r)la,ce  at  a lower  temjjS: nature. 
The  temperature  necessary  in  using  nickel  as  lizer 

is  so  high  that  a great  deal  of  decomposition  of  tlio 
benzene  takes  place. 


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21 


BIBLlOGRAPIiY 

I Reference  not  found  in  original, 

2,  Ber.  62;  478, 

3.  Ann.  Igl  363;  Comp.  Rend.  156:830 

4 Z.  f.  C^.  1366,  707. 

5 d.A.C.S,  954-35-139 

6 154:561  Comp. Rend, 

7 Hauben.  Chem  Zeit.  1905. 

B G-er  Pat  #157,573 

o Ber,  13:  457  Ber,. 13:  308 

10  Ann,  219:179 

I I Ann , 47:83. 

12  Ann.  2l6;301 

13  Ger  Pat,  #107,229 

14  Ber,  43:1035-38, 

15  Chemical  Reagents.  Illinois  University  Press. 

16  Ber.  6 794  ( 1673) 

17  Ann,  ^ 145  kBs3) 

If  Ber.  8 1402  Clf75) 

1 9 Ann . 237  151  ( 1 687 ) 


